CN103946291A - Additives for the hydrolytic stabilisation of polycondensates - Google Patents

Additives for the hydrolytic stabilisation of polycondensates Download PDF

Info

Publication number
CN103946291A
CN103946291A CN201280056408.XA CN201280056408A CN103946291A CN 103946291 A CN103946291 A CN 103946291A CN 201280056408 A CN201280056408 A CN 201280056408A CN 103946291 A CN103946291 A CN 103946291A
Authority
CN
China
Prior art keywords
polymkeric substance
mixture
alkyl
independently
another
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201280056408.XA
Other languages
Chinese (zh)
Inventor
L·波狄埃
T·斯米特
S·施洛
V·弗伦茨
R·范德米尔
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of CN103946291A publication Critical patent/CN103946291A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/916—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds

Abstract

The invention relates to a mixture containing at least one multi-functional chain extender with at least three reactive groups, as well as at least one monofunctional or difunctional hydrolytic stabilizer, said chain extender and hydrolytic stabilizers reacting with the end groups of polymers when the polymers are in a melted or solid state, with a chemical bond being formed. The invention also relates to the use of such mixtures as stabilizers for polymers, and to a method for the stabilization of polymers against losses in molecular weight in which an effective amount of such a mixture is added to the polymer.

Description

The additive that is used for the hydrolysis-stable of polycondensate
Describe
The present invention relates to the mixture that contains multifunctional chainextender and simple function or difunctionality hydrolysis stabilizer, it is for polymkeric substance.The invention still further relates to the mixture that contains multifunctional chainextender, simple function or difunctionality hydrolysis stabilizer and polymkeric substance.The invention still further relates to the described mixture that contains multifunctional chainextender and simple function or difunctionality hydrolysis stabilizer for the purposes of stabilization of polymer, and aspect loss of molecular weight the method for stabilization of polymer.
In claims, specification sheets and embodiment, can find other embodiment of the present invention.Obviously, above-mentionedly about the feature of theme of the present invention and the feature that will explain hereinafter, not only can use according to described separately particular combination, and can be used in combination according to other, and not exceed scope of the present invention.Of the present invention other preferably and separately highly preferred embodiment be that all features of wherein theme of the present invention have preferably and those of implication very preferably separately.
Initial exploitation chainextender is to obtain the polycondensate with high molecular in order to extrude via reactivity.For example, WO98/47940A1 has described difunctionality hexanolactam chainextender, its polyester for the preparation of high molecular and polymeric amide.
The multifunctional chainextender with three or more reactive groups causes the structure of branching.So, in polymeric matrix, using this additive not only to cause chain extension, and often cause branching phenomenon, this has significantly increased the viscosity that adds man-hour in melt.This additive is for example referring to US5, and 354,802, it is for for example polyester or polymeric amide.
WO2004/067629A1 has described the chainextender of dilute form for the purposes of inert support polymkeric substance.
US6,984,694B2 has described the multipolymer of (methyl) Acrylic Acid Monomer, vinylbenzene and/or (methyl) Acrylic Acid Monomer of containing epoxy functional as the purposes of chainextender.
Carbon imide is called hydrolysis stabilizer, for example, referring to US5, and 439,952, EP799843A1 or EP1262511A2.But, the common toxigenous by product of this application, for example phenyl isocyanate.Problem about toxicity is to avoid by the carbon imide with oligomeric or polymerization.
For example, DE3217440A1 has described the polyethylene terephthalate with improved hydrolytic resistance, and it contains poly-carbon imide.
DE19809634A1 has described and has prepared the method for carbon imide and contain carbon imide and the mixture of polyester or urethane.
WO2005/111048A1 has described the carbon imide containing via urea groups keyed jointing, and the mixture of they and polymkeric substance.
EP0 507 407A1 have described the polyfunctional water dispersible linking agent based on oligomeric, and it contains carbon imide and other reactive functional groups, for example heterogeneous ring compound.Water dispersion, emulsion or the solution of these linking agents have been described in addition, and the method for preparing described linking agent.
The inventor's undocumented patent application EP11158914.9 described contain at least one heterocycle shape end group oligomeric carbon imide as stablizer the purposes for polymkeric substance.
US4,385,144 described there is 10-50 carbon atom epoxy group(ing) paraffinic hydrocarbons in PET for improvement of the processing characteristics of polymkeric substance.
US4,393,156 and US4,393,158 have described epoxy radicals silicone hydride and epoxy group(ing) siloxanes for the purposes at stabilized polyester carbonic ether or aromatic polycarbonate aspect hydrolysis.
Alkyl ketene dimer is generally used for making paper or fiber hydrophobization, for example, referring to US5, and 028,236 or WO92/15746A1.
JP2007023100A2 has described the purposes of alkyl ketene dimer in aliphatic polyester stable.
US3,770,693 and US4,123,419 have described azoles alkane is the purposes for ester polymer (multipolymer) as stablizer, especially for polyester-polyurethane.
Polymkeric substance, polycondensation polymer for example, for example polyester, at high temperature degrades via hydrolysis conventionally.The processing in the situation that such situation for example deriving from polymkeric substance in heating and has moisture simultaneously.The hydrolysis of polymkeric substance causes molecular weight to reduce and melt viscosity reduces, and damages the mechanical property of polymkeric substance simultaneously.Described effect has seriously limited the application of these hydrolyzable polymkeric substance, causes in addition the high drying cost before polymer processing.
So, the object of this invention is to provide the stablizer for polymkeric substance, it can reduce degraded and alleviate hydrolysis.Specific purposes of the present invention are any reductions that suppress polymkeric substance melt viscosity between processing period.
Described object realizes by mixture (M), and it contains:
A. at least one has the multifunctional chainextender (K) of at least three reactive groups, and
B. at least one simple function or dual functional hydrolysis stabilizer (H),
Wherein, chainextender (K) and hydrolysis stabilizer (H) react to form chemical bond with polymkeric substance (P) end group in molten state or solid-state polymkeric substance (P).Preferably, chainextender (K) reacts with polymkeric substance (P) end group in polymkeric substance (P) in molten state, and hydrolysis stabilizer (H) reacts with polymkeric substance (P) end group in molten state or solid-state polymkeric substance (P).
For the purposes of the present invention, about C a-C bthe statement of type represents to have compound or the substituting group of particular carbon atom number.Carbon atom number can be selected from the gamut of a-b, comprises a and b, and a is that at least 1, b is always greater than a.About compound or substituent other explanation, be by C a-C bthe statement of-V type is carried out.Here, V represents classification or the substituent classification of compound, for example alkylate or alkyl substituent.
Halogen represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, particularly preferably fluorine or chlorine.
Implication separately for various substituent universal expression modes is as follows:
C 1-C 20alkyl: straight chain or branching there is the hydrocarbon structure part of 20 carbon atoms, for example C at the most 1-C 10alkyl or C 11-C 20alkyl, preferably C 1-C 10alkyl, for example C 1-C 3alkyl, for example methyl, ethyl, propyl group, sec.-propyl; Or C 4-C 6alkyl, normal-butyl, sec-butyl, the tertiary butyl, 1,1-dimethyl ethyl, amyl group, 2-methyl butyl, 1,1-dimethyl propyl, 1,2-dimethyl propyl, 2,2-dimethyl propyl, 1-ethyl propyl, hexyl, 2-methyl amyl, 3-methyl amyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 2-ethyl-butyl, 1,1,2-trimethylammonium propyl group, 1,2,2-trimethylammonium propyl group, 1-ethyl-1-methyl-propyl, 1-Ethyl-2-Methyl propyl group; Or C 7-C 10alkyl, for example heptyl, octyl group, 2-ethylhexyl, 2,4,4-tri-methyl-amyl, 1,1,3,3-tetramethyl butyl, nonyl or decyl, and their isomer.
C 2-C 20-alkenyl: the thering is 2-20 carbon atom and there is the hydrocarbon structure part of two keys in any desired location of undersaturated, straight chain or branching, for example C 2-C 10alkenyl or C 11-C 20alkenyl, preferably C 2-C 10alkenyl, for example C 2-C 4alkenyl, vinyl for example, 1-propenyl, 2-propenyl, 1-methyl ethylene, 1-butylene base, crotyl, 3-butenyl, 1-methyl-1-propylene base, 2-methyl-1-propylene base, 1-methyl-2-propenyl, 2-methyl-2-propenyl, or C 5-C 6-alkenyl, 1-pentenyl for example, pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl isophthalic acid-butenyl, 2-methyl-1-butene thiazolinyl, 3-methyl-1-butene base, 1-methyl-2-butene base, 2-methyl-2-butene base, 3-methyl-2-butene base, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1, 1-dimethyl-2-propenyl, 1, 2-dimethyl-1-propenyl, 1, 2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentene thiazolinyl, 2-methyl-1-pentene thiazolinyl, 3-methyl-1-pentene thiazolinyl, 4-methyl-1-pentene base, 1-methyl-pentenyl, 2-methyl-pentenyl, 3-methyl-pentenyl, 4-methyl-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1, 1-dimethyl-crotyl, 1, 1-dimethyl-3-butenyl, 1, 2-dimethyl-1-butylene base, 1, 2-dimethyl-crotyl, 1, 2-dimethyl-3-butenyl, 1, 3-dimethyl-1-butylene base, 1, 3-dimethyl-crotyl, 1, 3-dimethyl-3-butenyl, 2, 2-dimethyl-3-butenyl, 2, 3-dimethyl-1-butylene base, 2, 3-dimethyl-crotyl, 2, 3-dimethyl-3-butenyl, 3, 3-dimethyl-1-butylene base, 3, 3-dimethyl-crotyl, 1-ethyl-1-butylene base, 1-ethyl-crotyl, 1-ethyl-3-butenyl, 2-ethyl-1-butylene base, 2-ethyl-crotyl, 2-ethyl-3-butenyl, 1, 1, 2-trimethylammonium-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-Ethyl-2-Methyl-1-propenyl, or 1-Ethyl-2-Methyl-2-propenyl, and C 7-C 10alkenyl, for example isomer of heptenyl, octenyl, nonene base or decene base.
C 2-C 20alkynyl: the thering is 2-20 carbon atom and there is the hydrocarbyl group of triple bond in any desired location of straight chain or branching, for example C 2-C 10alkynyl or C 11-C 20alkynyl, preferably C 2-C 10alkynyl, for example C 2-C 4alkynyl, ethynyl for example, 1-proyl, 2-propynyl, ethyl acetylene base, 2-butyne base, 3-butynyl, 1-methyl-2-propynyl, or C 5-C 7-alkynyl, 1-pentynyl for example, valerylene base, 3-pentynyl, 4-pentynyl, 1-methyl-2-butyne base, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl isophthalic acid-butynyl, 1, 1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexin base, 2-hexin base, 3-hexin base, 4-hexin base, 5-hexin base, 1-methyl-valerylene base, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentene alkynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentene alkynyl, 4-methyl-valerylene base, 1, 1-dimethyl-2-butyne base, 1, 1-dimethyl-3-butynyl, 1, 2-dimethyl-3-butynyl, 2, 2-dimethyl-3-butynyl, 3, 3-dimethyl-ethyl acetylene base, 1-ethyl-2-butyne base, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl, or 1-ethyl-1-methyl-2-propynyl, and C 7-C 10alkynyl, for example isomer of heptyne base, octyne base, n-heptylacetylene base, decynyl.
C 3-C 15cycloalkyl: the stable hydrocarbon group with 3-15 carboatomic ring atom of monocycle, preferably C 3-C 8cycloalkyl, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl or ring octyl group, or saturated or unsaturated ring-type system, for example norcamphyl or norbornene.
Aryl: the aromatic ring system that contains 6-14 carbocyclic ring member of monokaryon to three core, for example phenyl, naphthyl or anthryl, preferably monokaryon is to double-core, particularly preferably the aromatic ring system of monokaryon.
C 1-C 20alkoxyl group represents the straight chain or the alkyl with 1-20 carbon atom (as mentioned above) of branching, for example C that via Sauerstoffatom (O-), connect 1-C 10alkoxyl group or C 11-C 20alkoxyl group, preferably C 1-C 10alkoxyl group, particularly preferably C 1-C 3alkoxyl group, for example methoxyl group, oxyethyl group, propoxy-.
Heteroatoms is phosphorus, oxygen, nitrogen or sulphur, preferred oxygen, nitrogen, sulphur, and wherein their free valence bond optionally meets with H atom.
In a specific embodiments of the present invention, chainextender (K) is to be selected from homopolymer and the multipolymer that contains at least three epoxy group(ing), at least three aziridine groups or at least three anhydride groups.
The homopolymer that contains at least three epoxy group(ing) and multipolymer are particularly preferably as chainextender (K).These chainextenders (K) very particularly preferably relate to the multipolymer that contains at least three epoxy group(ing), the multipolymer of the epoxy functional that particularly contains vinylbenzene and (methyl) acrylate monomer with polymerized form.
The example of these chainextenders (K) very preferably and preparation method thereof is referring to US6,984,694B2.
Preferred chainextender (K) is that at least one has the monomer of at least one epoxy group(ing) and the copolymerization product of at least one vinylbenzene and/or (methyl) acrylate monomer.For example these comprise epoxy functional (methyl) acrylate monomer and non-epoxy functional styrene monomer and/or with the combination of (methyl) acrylate monomer.For the object of the invention, term (methyl) acrylate monomer not only comprises acryl ester monomer (acrylate monomer), and comprises methacryloyl ester monomer (methacrylate monomer).
The example of (methyl) acrylate monomer of epoxy functional comprises those that contain 1,2-epoxy group(ing), for example vinylformic acid glycidyl esters and methyl propenoic acid glycidyl base ester.The monomer of other epoxy functional comprises allyl glycidyl ether, ethylacrylic acid glycidyl esters and methylene-succinic acid glycidyl esters.
Can comprise (ignoring epoxy functional) for acrylate of the present invention and methacrylate monomer: methyl acrylate, vinylformic acid ethyl ester, vinylformic acid n-propyl ester, vinylformic acid n-hexyl ester, vinylformic acid n-octyl ester, methyl methacrylate, methacrylic acid ethyl ester, methacrylic acid n-propyl ester, methyl methacrylate basic ring polyhexamethylene, IBOMA, butyl acrylate cores, methacrylic acid butyl ester, methacrylic acid isobutyl, vinylformic acid cyclohexyl ester, methacrylic acid cyclohexyl ester, isobornyl acrylate, IBOMA, and their mixture.
Preferred non-functionalized acrylate and methacrylic ester comprise butyl acrylate cores, methacrylic acid butyl ester, methyl methacrylate, methacrylic acid isobutyl, vinylformic acid cyclohexyl ester, methacrylic acid cyclohexyl ester, isobornyl acrylate, IBOMA, and their mixture.
Can comprise vinylbenzene for styrene monomer of the present invention, alpha-methyl styrene, Vinyl toluene, p-methylstyrene, t-butyl styrene, o-chloro-styrene, vinyl pyridine, and their mixture.In a specific embodiments, monomer is to be selected from vinylbenzene and alpha-methyl styrene.
Particularly preferred copolymerization product contains at least one monomer that is selected from vinylformic acid glycidyl esters and methyl propenoic acid glycidyl base ester, and contains the monomer that at least one is selected from vinylbenzene, methyl methacrylate, methyl acrylate, butyl acrylate cores and vinylformic acid (ethyl hexyl) ester.
Preferably, at least one copolymerization product with the monomer of at least one epoxy group(ing) and at least one vinylbenzene and/or (methyl) acrylate monomer has the epoxide equivalent weight (EEW) of 180-2800g/mol, preferred 190-1400g/mol, particularly preferably 200-700g/mol.Preferably, the Efn value (Efn=Mn/EEW) of described copolymerization product is to be less than 30, and preferably 2-20, is particularly preferably 3-10.In addition preferably, the Efw value (Efw=Mw/EEW) of described copolymerization product is to be less than 140, and preferably 3-65, is particularly preferably 6-45.Efn is several equal epoxy functional degree, and Efw is weight average epoxy functional degree.
Preferably, at least one mumber average molar mass (Mn) with the monomer of at least one epoxy group(ing) and the copolymerization product of at least one vinylbenzene and/or (methyl) acrylate monomer is less than 6000g/mol, preferably 1000-5000g/mol, is particularly preferably 1500-4000g/mol.In addition preferably, the weight-average molar mass of these copolymerization products (Mw) is to be less than 25000g/mol, preferably 1500-18000g/mol, particularly preferably 3000-13000g/mol, particularly 4000-8500g/mol.
EEW value is corresponding to the quality with the copolymerization product of 1 equivalent epoxy functional degree, it is to detect (for standard detecting method (1990) the detection method B of the epoxy group content of epoxy resin) according to ASTM D1652-90, or for example according to US6,552,144B1 detects from the mass balance of the monomer with epoxy group(ing) used.
The molecular weight distribution of copolymerization product is to detect by gel permeation chromatography (GPC)., first copolymerization product is dissolved in tetrahydrofuran (THF) (THF) for this reason, then injects GPC equipment.The example of operable GPC equipment is Waters2695 equipment, and it has Waters2410 refractive index (RI) detector.Operable post is PLGEL MIXED B post, and it has monitoring post, allows especially to detect Mn and Mw value.
At least one has the monomer of at least one epoxy group(ing) and the copolymerization product of at least one vinylbenzene and/or (methyl) acrylate monomer can be purchased, for example conduct product obtains from BASF SE.
In another preferred embodiment of mixture of the present invention, hydrolysis stabilizer (H) is selected from:
A. the oligomeric carbon imide of general formula (I):
A wherein 1and A 2being identical or different, is the hydrocarbyl group with 3-20 carbon atom independently of one another, preferably contains cyclic hydrocarbon structures part, particularly C 3-C 14cycloalkylidene, arylidene,
B 1and B 2being identical or different, is heterogeneous ring compound, C independently of one another 1-C 30-ol, Aethoxy Sklerol, polyesterols, amine, polyetheramine, polyesteramine, mercaptan, polyethers mercaptan, polyester mercaptan,
N is the integer within the scope of 2-100, preferably in the scope of 2-50, and in the scope particularly preferably in 2-20, particularly in the scope of 2-10,
And, A wherein 1, A 2, B 1and B 2separately can be in any desired position by C 1-C 20alkyl, C 2-C 20alkenyl, C 2-C 20alkynyl, C 1-C 20alkoxyl group, ketonic oxygen (=O) or halogen replace, preferably by C 1-C 4alkyl replaces,
B. general formula (IIa) or simple function (IIb) or dual functional epoxy compounds:
Wherein
X 1, X 2and X 3being identical or different, is CH independently of one another 2, O, C (=O), OC (=O), C (=O) NH, preferably O or CH 2, O particularly preferably,
Y 1, Y 2and Y 3being identical or different, is singly-bound, C independently of one another 1-C 20alkylidene group, C 1-C 20alkenylene, arylidene, preferably singly-bound or C 1-C 20alkylidene group is particularly preferably C 1-C 20alkylidene group,
Z 1h, SiR 1r 2r 3, Si (OR 1) R 2r 3, Si (OR 1) (OR 2) R 3, Si (OR 1) (OR 2) (OR 3), preferred Si (OR 1) (OR 2) (OR 3),
Z 2and Z 3being identical or different, is singly-bound, SiR independently of one another 1r 2, Si (OR 1) R 2, Si (OR 1) (OR 2),
L 1singly-bound, O, CH 2,
R 1, R 2and R 3being identical or different, is C independently of one another 1-C 20alkyl, preferably C 1-C 10alkyl, particularly preferably C 1-C 4alkyl, particularly C 1-C 2alkyl,
R 20, R 21and R 22being identical or different, is H, C independently of one another 1-C 20alkyl, preferred H, or
R 20with R 21or R 22be dimethylene, trimethylene or tetramethylene together, so form the member ring systems of 5,6 or 7 yuan,
R 23, R 24and R 25being identical or different, is H, C independently of one another 1-C 20alkyl, preferred H, or
R 23with R 24or R 25be dimethylene, trimethylene or tetramethylene together, so form the member ring systems of 5,6 or 7 yuan,
C. the alkyl ketene dimer of general formula (III):
Wherein
R 41and R 42being identical or different, is H or C independently of one another 1-C 30alkyl, preferably H or C 4-C 20alkyl is particularly preferably H or C 6-C 18alkyl,
R 51and R 52being identical or different, is H or C independently of one another 1-C 30alkyl, preferably H or C 4-C 20alkyl is particularly preferably H or C 6-C 18alkyl,
D. general formula (IV) or heterogeneous ring compound (V):
Wherein
A is O or NR 16,
R 6h, C 1-C 20alkyl, aryl, C 3-C 15cycloalkyl, NR 26r 27,
Preferred H, C 1-C 10alkyl, propionyl, ethanoyl, crotonyl, particularly preferably H, C 1-C 4alkyl,
Particularly H, C 1-C 2alkyl,
R 16h, C 1-C 20alkyl, aryl, C 3-C 15cycloalkyl, halogen,
Preferably H, C 1-C 10alkyl, aryl,
Particularly preferably H, C 1-C 4alkyl, phenyl, tolyl,
R 26and R 27being identical or different, is H, C independently of one another 1-C 20alkyl, aryl, C 3-C 15cycloalkyl,
Preferred H, C 1-C 10alkyl, aryl,
Particularly preferably H, C 1-C 4alkyl, phenyl, tolyl,
R 7, R 8, R 9and R 10being identical or different, is H, C independently of one another 1-C 20alkyl, aryl, C 3-C 15cycloalkyl,
Preferred H, C 1-C 18alkyl, aryl, C 5-C 8cycloalkyl,
Particularly preferably H, C 1-C 4alkyl,
Particularly H, C 1-C 2alkyl,
R wherein 6and R 16separately can be in any desired position by C 1-C 20alkyl, C 2-C 20alkenyl, C 2-C 20alkynyl, C 1-C 20alkoxyl group, ketonic oxygen (=O) or halogen replace, preferably by C 1-C 4alkyl, C 2-C 10alkenyl, ketonic oxygen (=O) replace.
Other advantage of these hydrolysis stabilizers (H) is that they do not have disadvantageous effect to the melt viscosity of polymkeric substance, color, mist degree or smell.
Preferably, the selection of hydrolysis stabilizer (H) can significantly not increase melt viscosity during extruding, and preferably increases and is less than 20%, is particularly preferably less than 10%, carrys out realize target viscosity in fact in this way by adding chainextender (K).
The oligomeric carbon imide c of general formula (I) can be for example referring to EP0 507 407A1 or the inventor's unexposed patent application EP11158914, by well known to a person skilled in the art prepared by method.The method of the oligomeric carbon imide that general preparation contains at least one heterocycle shape end group comprises that for example vulcabond reacts with Aethoxy Sklerol with heterogeneous ring compound.
In a further preferred embodiment, the substituent A of the oligomeric carbon imide of general formula (I) 1and A 2contain following hydrocarbyl group:
Preferably, the substituent A of oligomeric carbon imide 1and A 2contain following hydrocarbyl group:
In a preferred embodiment of mixture of the present invention, the substituent B of carbon imide 1and B 2be to be selected from 3-12 unit, preferably 3-9 unit, the member ring systems of 5-7 unit particularly preferably, it has Sauerstoffatom, nitrogen-atoms and/or sulphur atom and has one or more rings (heterogeneous ring compound, heterocycle shape end group), aziridine for example, epoxide, thiirane, azirane, oxyethylene, thiirene, azetidine, trimethylene oxide, thiophene fourth ring, beta-lactam, β-lactone, thiophene fourth cyclic ketones (thiethanone), furans, pyrroline, dihydrofuran, dihydro-thiophene, tetramethyleneimine, tetrahydrofuran (THF), tetramethylene sulfide azoles alkane, dioxolane, oxa-thia ring, thiazolidine, tetrahydroglyoxaline, dithia ring, pyrazolidine, pyrazoline, azoles quinoline, thiazoline, tetrahydroglyoxaline, dioxole, oxazolone, pyrrolidone, butyrolactone, sulfo-butyrolactone, sulfo-butyrolactone, sulfo-butyryl thiolactone (thiobutyrothiolactone), oxazolidone, dioxolan-2-one, thiazolidone, dihydropyridine, tetrahydropyridine, pyrans, dihydropyrane, tetrahydropyrans, succinyl oxide, succinimide, sulfo-pyrans, dihydrogen phosphorothioate pyrans, tetrahydrochysene sulfo-pyrans, dihydro-pyrimidin, tetrahydropyrimidine, hexahydropyrimidine, two alkane, morpholine, thia morpholine, dithiane, triazine, wherein they have the chemical bond-linking according to any required mode in general formula (I), for example, be connected with the carbon atom of heterocycle or be connected with one of heteroatoms.
Particularly preferably be the saturated nitrogenous member ring systems of 5,6 or 7 yuan, it has the connection via theheterocyclic nitrogen atom or ring carbon atom, also can have one or two other nitrogen-atoms or Sauerstoffatom.They are very particularly preferably selected from following:
In an especially preferred embodiment, be below applicable to the substituting group of carbon imide: A 1=A 2and B 1=B 2.
General formula (IIa) and epoxy compounds b (IIb) and preparation method thereof are those skilled in the art's common practise, for example, referring to US4, and 385,144, US4,393,156 or US4,393,158.General formula (IIa) and epoxy compounds (IIb) can be purchased.
Alkyl ketene dimer c of general formula (III) and preparation method thereof is those skilled in the art's common practise, for example, referring to US5, and 028,236 or WO92/15746A1.The alkyl ketene dimer of general formula (III) can be purchased.
General formula (IV) and heterogeneous ring compound d (IV) ( oxazolidone and derivative thereof or isomer) and preparation method thereof be those skilled in the art's common practise, for example, referring to US3,770,693 or US4,123,419.General formula (IV) and heterogeneous ring compound (IV) can be purchased.
In mixture (M), the quantification between at least one multifunctional chainextender (K) and at least one simple function or dual functional hydrolysis stabilizer (H) can change according to application in wide region.For example relatively large chainextender (K) is for the application of the higher initial viscosity of needs, and for example PET circulates.Polymkeric substance must be exposed in the application under comparatively high temps and higher levels of humidity therein, and the ratio of hydrolysis stabilizer correspondingly increases.Those skilled in the art can set suitable ratio with suitable experiment.Quantification between K and H (weight) normally in the scope of 1:100-100:1, preferably 1:50-50:1, very preferably 1:20-20:1, particularly 1:10-10:1.
In another embodiment of mixture of the present invention, polymkeric substance (P) is polycondensate or addition polymer.Preferably, polymkeric substance is to be selected from polyester, polymeric amide, urethane, polycarbonate, and their multipolymer and/or mixture.Particularly, to be by stable polymkeric substance be selected from following: PET (polyethylene terephthalate), PBT (polybutylene terephthalate), PEN (Polyethylene Naphthalate), PC (polycarbonate), biodegradable aliphatic-aromatic copolyesters, biological polymer, and PA6 (nylon-6).Specially suitable biodegradable aliphatic-aromatic copolyesters is polybutylene adipic acid ester-copolymerization-terephthalate), and the biological polymer that can use is especially PLA (poly(lactic acid)) and PHA (polyhydroxyalkanoatefrom).Specially suitable mixture is PC/ABS (acrylonitrile-butadiene-styrene copolymer) mixture.The polymkeric substance that can certainly be contained circulation or regeneration by stable polymkeric substance.In a preferred embodiment of mixture of the present invention, polymkeric substance (P) contains hydroxyl end groups, amine end groups, carboxyl end groups or carboxylic end group, particularly carboxylic end group in addition.
The present invention also provides mixture (MP), and it contains:
A. at least one said mixture (M), and
B. in addition, at least one above-mentioned polymkeric substance (P).
In a preferred embodiment of mixture of the present invention (MP), it is 0.01-10 % by weight that at least one mixture (M) is added to the amount at least one polymkeric substance (P), preferred 0.1-5 % by weight, 0.1-2 % by weight particularly, the total amount meter based on polymkeric substance (P) and mixture (M).
The operation of mixture (M) being introduced to polymkeric substance (P) realizes by mixing each component conventionally.For example, mixing is that these are the methods that are generally used for providing to polymkeric substance additive by well known to a person skilled in the art that method carries out.Mixture in solid, liquid or solubilized form (M) is preferred for modification addition polymer or polycondensate.For this reason, when they are introduced into polymkeric substance by ordinary method, mixture (M) can be the form of solid or liquid adjustments, or powder.For example, can mention that mixture (M) is extruded at extrusion step, kneading, calendering, film, fiber is extruded here or blowing before or during with the mixing of polymkeric substance (P).Each component can be mixed before introducing technique, this carries out under the help of solvent or in the situation that not using solvent.Solvent can optionally be removed before introducing technique.Being used for can be referring to plastics additive handbook (Plastics Additive Handbook), the 5th edition, Hanser Verlag, ISBN1-56990-295-X with other example of additive improved or stabilization of polymer.The polymkeric substance that contains additive can be for example the form of granulated material, ball material, powder, film or fiber.
The polymer moulding that contains mixture (M) is by well known to a person skilled in the art that method produces.Particularly, polymer moulding can be via extruding or the processing of coextrusion, chemical combination, granulated material or ball material, injection moulding, blowing or mediate and produce.Preferably via extruding or coextrusion processes to obtain film (referring to Saechtling Kunststoff Taschenbuch[plastics handbook], the 28th edition, Karl Oberbach, 2001).
Polymkeric substance or polymer moulding can contain at least one other common commercially available additive in addition, are preferably selected from: tinting material, antioxidant, other stablizer is hindered amine light stabilizer (HALS) for example, UV absorption agent, nickel quencher, metal passivator, strongthener and filler, antifogging agent, microbicide, acid scavenger, static inhibitor, for the IR absorption agent of long wave IR radiation, antiblocking agent is SiO for example 2, light scattering agent is MgO or TiO for example 2, and inorganic or organic tamper (for example aluminium flake).Can use equally other not chainextender or the hydrolysis stabilizer in mixture (M) scope.
The present invention also provides the purposes of said mixture (M), and wherein they,, as stablizer for above-mentioned polymkeric substance (P), are particularly provided for aspect loss of molecular weight and/or hydrolysis, playing the purposes of stabilization.
The present invention also provides the method for a kind of stabilization of polymer (P), and particularly stable for loss of molecular weight and/or hydrolysis aspect, wherein adds polymkeric substance (P) by the mixture of significant quantity (M).Preferably, the amount that adds described (M) in polymkeric substance (P) is 0.01-10 % by weight, based on polymkeric substance (P) and the total amount meter of mixture (M).For the object of stabilising method of the present invention, above-mentioned additive is added in polymkeric substance (P) in addition.
The invention provides the mixture (M) polymkeric substance to stabilising effect, wherein they have reduced the degraded of polymkeric substance and have alleviated the hydrolysis of polymkeric substance, particularly between their processing period.
Following examples are further explained the present invention, but do not limit the scope of the invention.
Embodiment:
The polyethylene terephthalate with intrinsic viscosity 69ml/g (PET) for the production of Biaxially oriented film is purchased from Mitsubishi Polyester Film GmbH, Wiesbaden.PET has the carboxyl end groups (about 21mmol/kg) of lower concentration.Acid number is to obtain by the corresponding PET solution of the solvent mixture titration being made by chloroform/cresols.
Additive is extruded under various concentration at the temperature of 260 ℃ together with PET.Then the film of gained is exposed at the temperature (110 ℃) and high humidity (100%) of rising, and stores 2 days or 5 days.The degraded of polymkeric substance is by detecting before storing and the concentration determination of intrinsic viscosity (IV) and/or the acid end group in PET afterwards.The detection of IV (unit is mg/l) is by using miniature Ubbelohde capillary viscosimeter to carry out, and wherein uses the 1:1 mixture of phenol and orthodichlorobenzene as solvent.
It is that 118ml/g and acid number are about 25mmol/kg that PBT matrix used contains intrinsic viscosity b4520 (BASF SE).Coextrusion is for additive is added to PBT, and prepares moulded product to carry out tension test.Detection after intrinsic viscosity and acid end group store before storing and under 110 ℃ and 100% humidity with part sample.
Except as otherwise noted, reference sample (Ref.) used contains corresponding polymkeric substance, for example PET or PBT, and it is extruded, but not containing hydrolysis stabilizer or chainextender.
Comparative example 1:Joncryl product
This embodiment is used two kinds of Joncryl:
aDR4368 (phenylethylene ethylene/propenoic acid ester copolymer, Mw=6800g/mol, EEW=285g/mol)
aDR4300 (phenylethylene ethylene/propenoic acid ester copolymer, Mw=5500g/mol, EEW=445g/mol)
Table 1.1 has compared limiting viscosity and the acid end group concentration of comparing with reference sample (Ref.).
Table 1.1
Described consumption be based on total amount meter with polymkeric substance.The concentration of acid end group be based on total amount meter with polymkeric substance.
product has significantly increased the viscosity after film is extruded.But, if avoid the unfavorable viscosity rise between processing period, only can use lower concentration (0.2 % by weight for example 4300), and these concentration can not prevent the increase of the acid end group between the shelf lives.
Table 1.2 has been listed the variation of intrinsic viscosity between the shelf lives of film.These data are identical with table 1.1.But selected reference (reference variable) is the intrinsic viscosity of each sample before storing now.
Table 1.2
Obviously use separately can not effectively suppress the degraded of polymkeric substance between the shelf lives.In all cases, intrinsic viscosity has reduced 20-25% two days later storing, and does not add time polymkeric substance as broad as long.
The embodiment of the present invention 2: alkyl ketene dimer (AKD) compound
Table 2.1 and 2.2 shows with the AKD with formula (III ') and carries out for example stable aspect hydrolysis of PET and PBT of polymkeric substance:
Wherein
R 41, R 42h, (CH 2) 15-CH 3,
R 51, R 52h, (CH 2) 15-CH 3,
Its Chinese style (III ') represents the mixture of isomer, wherein R 41and R 42and R separately 51and R 52when different, be H or (CH 2) 15-CH 3.
Table 2.1 has compared the effect of independent use AKD.
Table 2.1
The amount of described AKD is the total amount meter based on AKD and polymkeric substance.
The concentration of acid end group is the total amount meter based on AKD and polymkeric substance.
AKD has suppressed the increase of acid end group between the shelf lives.But intrinsic viscosity can significantly not increase during extruding.
Table 2.2 compared independent use AKD with and and chainextender the effect that ADR4300 is used in combination.Obviously, the combination of hydrolysis stabilizer (H) and chainextender (H) has synergy.
Table 2.2
Described AKD and the amount of ADR4300 be in each case based on AKD and/or the total amount meter of ADR4300 and polymkeric substance.
The concentration of acid end group be based on AKD and/or the total amount meter of ADR4300 and polymkeric substance.
The embodiment of the present invention 3: oxazolidone
Table 3.1 has shown by formula (IV ') the result that oxazolidone is realized in PBT:
A=O wherein, R 6=R 7=R 8=R 9=R 10=H.
Table 3.1
Described the amount of oxazolidone be based on the total amount meter of oxazolidone and polymkeric substance.
The concentration of acid end group be based on the total amount meter of oxazolidone and polymkeric substance.
In table 3.1, show for the effect of oxazolidone in PBT, it is for initial viscosity and the little effect that reduces acid end group concentration between the shelf lives, can with chainextender ( aDR4300) effect is collaborative, as the AKD in the embodiment of the present invention 2.
The embodiment of the present invention 4: single epoxy group(ing) and monocycle TMOS compound
Table 4.1 and 4.2 shown PET or PBT at a kind of epoxy radicals silicone hydride, be the result of extruding under 3-glycidoxy propyl-triethoxysilicane exists, described silane compound can be used as gF82 (Wacker Chemie AG) obtains.These tables also comprise that use 1,2-epoxy group(ing) decane is as the result of hydrolysis stabilizer.
These two kinds of additives (hydrolysis stabilizer) have all significantly been alleviated the degraded of polyester between the shelf lives, and can not increase initial characteristic viscosity number.
Table 4.1 (PET)
The concentration of described additive is the total amount meter based on additive and polymkeric substance.
The concentration of acid end group is the total amount meter based on additive and polymkeric substance.
Table 4.2 (PBT)
The concentration of described additive is the total amount meter based on additive and polymkeric substance.
The concentration of acid end group is the total amount meter based on additive and polymkeric substance.
Also additive can be added at the form with masterbatch, thereby obtain in final product the advantageous effects as hydrolysis stabilizer.For this reason, the first step is to prepare masterbatch, wherein in the PBT of about 800g, extrudes hydrolysis stabilizer, and the amount of described hydrolysis stabilizer is in order to provide via reacting the necessary amount of the PBT having extruded with complete stability 5kg with acid end group (about 30mmol/kg).
Acid end group concentration in masterbatch stores detection two days later before storing and under 110 ℃ and 100% humidity.
Then masterbatch is again extruded in second step in PBT (total amount of raw material is 5kg).Acid end group concentration in final product also stores detection two days later before storing and under 110 ℃ and 100% humidity.Table 4.3 is listed following result:
Table 4.3 (PBT masterbatch and final product)
The concentration of described additive is the total amount meter based on additive and polymkeric substance.
The concentration of acid end group is the total amount meter based on additive and polymkeric substance.
Monocycle oxycompound causes the minimum increase of initial viscosity during extruding especially, thus can be advantageously with the invention described above embodiment 2 and 3 in chainextender synergistic combination use..
Table 4.4 has compared independent use 1,2-epoxy group(ing) decane and its with effect when ADR4300 is used in combination.
Table 4.4
The concentration of described additive is the total amount meter based on additive and polymkeric substance.
The concentration of acid end group is the total amount meter based on additive and polymkeric substance.

Claims (14)

1. a mixture (M), it contains:
A. at least one has the multifunctional chainextender (K) of at least three reactive groups, and
B. at least one simple function or dual functional hydrolysis stabilizer (H),
Wherein, chainextender (K) and hydrolysis stabilizer (H) react to form chemical bond with polymkeric substance (P) end group in molten state or solid-state polymkeric substance (P).
2. according to the mixture of claim 1, wherein chainextender (K) is to be selected from homopolymer or the multipolymer that contains at least three epoxy group(ing), at least three aziridine groups or at least three anhydride groups.
3. according to the mixture of claim 2, the chainextender (K) that wherein contains at least three epoxy group(ing) comprises the multipolymer of the epoxy functional that contains vinylbenzene and (methyl) Acrylic Acid Monomer with polymerized form.
4. according to the mixture of claim 1-3, wherein hydrolysis stabilizer (H) is selected from:
A. the oligomeric carbon imide of general formula (I):
A wherein 1and A 2being identical or different, is the hydrocarbyl group with 3-20 carbon atom independently of one another,
B 1and B 2being identical or different, is heterogeneous ring compound, C independently of one another 1-C 30alcohol, Aethoxy Sklerol, polyesterols, amine, polyetheramine, polyesteramine, mercaptan, polyethers mercaptan, polyester mercaptan,
N is the integer within the scope of 2-100,
And, A wherein 1, A 2, B 1and B 2separately can be in any desired position by C 1-C 20alkyl, C 2-C 20alkenyl, C 2-C 20alkynyl, C 1-C 20alkoxyl group, ketonic oxygen (=O) or halogen replace,
B. general formula (IIa) or simple function (IIb) or difunctional epoxide based compound:
Wherein
X 1, X 2and X 3being identical or different, is CH independently of one another 2, O, C (=O), OC (=O), C (=O) NH,
Y 1, Y 2and Y 3being identical or different, is singly-bound, C independently of one another 1-C 20alkylidene group, C 1-C 20alkenylene, arylidene,
Z 1h, SiR 1r 2r 3, Si (OR 1) R 2r 3, Si (OR 1) (OR 2) R 3, Si (OR 1) (OR 2) (OR 3),
Z 2and Z 3being identical or different, is singly-bound, SiR independently of one another 1r 2, Si (OR 1) R 2, Si (OR 1) (OR 2),
L 1singly-bound, O, CH 2,
R 1, R 2and R 3being identical or different, is C independently of one another 1-C 20alkyl,
R 20, R 21and R 22being identical or different, is H, C independently of one another 1-C 20alkyl, or
R 20with R 21or R 22be dimethylene, trimethylene or tetramethylene together, so form the member ring systems of 5,6 or 7 yuan,
R 23, R 24and R 25being identical or different, is H, C independently of one another 1-C 20alkyl, or
R 23with R 24or R 25be dimethylene, trimethylene or tetramethylene together, so form the member ring systems of 5,6 or 7 yuan,
C. the alkyl ketene dimer of general formula (III):
Wherein
R 41and R 42being identical or different, is H or C independently of one another 1-C 30alkyl,
R 51and R 52being identical or different, is H or C independently of one another 1-C 30alkyl,
D. general formula (IV) or heterogeneous ring compound (V):
Wherein
A is O or NR 16,
R 6h, C 1-C 20alkyl, aryl, C 3-C 15cycloalkyl, NR 26r 27,
R 16h, C 1-C 20alkyl, aryl, C 3-C 15cycloalkyl, halogen,
R 26and R 27being identical or different, is H, C independently of one another 1-C 20alkyl, aryl, C 3-C 15cycloalkyl,
Preferred H, C 1-C 10alkyl, aryl,
Particularly preferably H, C 1-C 4alkyl, phenyl, tolyl,
R 7, R 8, R 9and R 10being identical or different, is H, C independently of one another 1-C 20alkyl, aryl, C 3-C 15cycloalkyl,
R wherein 6and R 16separately can be in any desired position by C 1-c 20alkyl, C 2-C 20alkenyl, C 2-C 20alkynyl, C 1-C 20alkoxyl group, ketonic oxygen (=O) or halogen replace.
5. according to the mixture of claim 1-4, wherein polymkeric substance (P) is polycondensate or addition polymer.
6. according to the mixture of claim 5, wherein polymkeric substance (P) is to be selected from polyester, polymeric amide, urethane, polycarbonate, and their multipolymer, and the mixture of described polymkeric substance.
7. according to the mixture of claim 5, wherein polymkeric substance (P) is PET, PBT, PEN, PC, biodegradable aliphatic-aromatic copolyesters, biological polymer or PA6.
8. according to the mixture of claim 1-7, wherein polymkeric substance (P) contains hydroxyl end groups, amine end groups, carboxyl end groups or carboxylic end group.
9. a mixture (MP), it contains:
A. at least one is according to the mixture of claim 1-8 (M), and
B. in addition, according to the polymkeric substance of claim 1-8 (P).
10. according to the mixture of claim 1-8 (M), as stablizer, be used for the purposes of polymkeric substance (P).
11. according to the purposes of claim 10, stable for aspect loss of molecular weight or hydrolysis.
The method of 12. 1 kinds of stabilization of polymer (P) aspect loss of molecular weight or hydrolysis, comprise to polymkeric substance (P) add significant quantity according to the mixture of claim 1-8 (M).
13. according to the method for claim 12, wherein to mixture (M), adds the polymkeric substance (P) of 0.01-10 % by weight, the total amount meter based on polymkeric substance (P) and mixture (M).
14. according to the method for claim 12 or 13, wherein to polymkeric substance (P), adds the following additive of being selected from of significant quantity in addition: tinting material, antioxidant, other stablizer, UV absorption agent, nickel quencher, metal passivator, strongthener and filler, antifogging agent, microbicide, acid scavenger, static inhibitor, IR absorption agent for long wave IR radiation, antiblocking agent, light scattering agent, and inorganic or organic tamper.
CN201280056408.XA 2011-11-17 2012-11-13 Additives for the hydrolytic stabilisation of polycondensates Pending CN103946291A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP11189569.4 2011-11-17
EP11189569 2011-11-17
PCT/EP2012/072489 WO2013072310A1 (en) 2011-11-17 2012-11-13 Additives for the hydrolytic stabilisation of polycondensates

Publications (1)

Publication Number Publication Date
CN103946291A true CN103946291A (en) 2014-07-23

Family

ID=47146429

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201280056408.XA Pending CN103946291A (en) 2011-11-17 2012-11-13 Additives for the hydrolytic stabilisation of polycondensates

Country Status (6)

Country Link
EP (1) EP2780407A1 (en)
JP (1) JP2014533752A (en)
KR (1) KR20140103956A (en)
CN (1) CN103946291A (en)
IN (1) IN2014CN03735A (en)
WO (1) WO2013072310A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109971007A (en) * 2019-04-01 2019-07-05 江南大学 A kind of normal-temperature solidification polyurethane class anti-fog thin film and preparation method thereof

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11001705B2 (en) 2015-12-25 2021-05-11 Toyobo Co., Ltd. Polyester resin composition, light-reflector component containing same, light reflector, and method for producing polyester resin composition
JP6642701B2 (en) 2017-02-02 2020-02-12 東洋紡株式会社 Polyester resin composition, light reflector component and light reflector containing the same
WO2018143099A1 (en) 2017-02-02 2018-08-09 東洋紡株式会社 Polyester resin composition, and light reflector component and light reflector including same
WO2019188921A1 (en) 2018-03-26 2019-10-03 東洋紡株式会社 Polyester resin composition, and component for optically reflective member and optically reflective member containing same
EP3670180A1 (en) * 2018-12-17 2020-06-24 LANXESS Deutschland GmbH Multi-layer system made from at least 3 polyester layers, its preparation and use
KR102421034B1 (en) 2020-05-28 2022-07-14 에코밴스 주식회사 Method for preparing biodegradable polyester resin and bioderadable polyester resin therefrom
JP7282124B2 (en) 2020-05-28 2023-05-26 エコバンス カンパニー・リミテッド Biodegradable polyester resin composition, nonwoven fabric and film, and method for producing the same
WO2023229214A1 (en) * 2022-05-21 2023-11-30 에코밴스 주식회사 Biodegradable polyester resin composition and biodegradable molded article comprising same
KR20230162745A (en) * 2022-05-21 2023-11-28 에코밴스 주식회사 Biodegradable polyester resin composition and preperation method thereof
WO2023229216A1 (en) * 2022-05-21 2023-11-30 에코밴스 주식회사 Biodegradable molded article and biodegradable polyester resin composition

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0628541A1 (en) * 1993-06-08 1994-12-14 BASF Aktiengesellschaft Carbodiimides and/or oligomeric polycarbodiimides based on 1,3-bis-(1-methyl-1-isocyanatoethyl)-benzene, process for their preparation and their use as stabilizer against hydrolysis
CN1232820A (en) * 1998-03-06 1999-10-27 巴斯福股份公司 Carbodiimides and their preparation
CN101928446A (en) * 2008-11-11 2010-12-29 三菱聚酯薄膜有限公司 Biaxially oriented hydrolysis resistant polyester film and method for production of same and use of same
CN101955633A (en) * 2009-05-15 2011-01-26 三菱聚酯薄膜有限公司 Biaxially stretched polyester film containing a decarboxylation catalyst and method for production of same and use of same in electrical insulation applications

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3770693A (en) 1964-10-09 1973-11-06 Baychem Corp Stabilization of polyesterurethanes with 2-imino-oxazolidines
US4123419A (en) 1977-08-26 1978-10-31 Mobay Chemical Corporation Stabilized thermoplastic polyesterurethanes
US4393158A (en) 1981-07-20 1983-07-12 General Electric Company Hydrolytically stable polycarbonate compositions
US4393156A (en) 1981-07-20 1983-07-12 General Electric Company Hydrolytically stable polyester-carbonate compositions
DE3217440A1 (en) 1982-05-08 1983-11-10 Basf Ag, 6700 Ludwigshafen Polyethylene terephthalate having improved resistance to hydrolysis, and the use thereof
US4385144A (en) 1982-07-12 1983-05-24 Ethyl Corporation Polyester composition
DE3826769A1 (en) 1988-08-06 1990-02-15 Bayer Ag TREATMENT OF POLYAMIDE FIBERS
AU657123B2 (en) 1991-03-01 1995-03-02 E.I. Du Pont De Nemours And Company Surface treated aramid fibers and a process for making them
NL9100578A (en) 1991-04-03 1992-11-02 Stahl Holland Bv MULTI-FUNCTIONAL WATER-DISPERSIBLE CROSS-CONTAINERS.
US5354802A (en) 1993-02-11 1994-10-11 Polyplastics Co., Ltd. Resin composition for blow molding and blow molded item made therefrom
US5439952A (en) 1993-12-21 1995-08-08 The Thompson Minwax Company Self-curing coating composition exhibiting reduced discoloration upon storage
JP3733170B2 (en) 1996-04-02 2006-01-11 日清紡績株式会社 Polyurethane resin
WO1998047940A1 (en) 1997-04-22 1998-10-29 Dsm N.V. High-molecular polyamide
ATE455797T1 (en) 1999-07-14 2010-02-15 Basf Corp METHOD FOR THE CONTINUOUS PRODUCTION OF EPOXY (METH)ACRYLIC STYRENE POLYMERS AND THEIR USE IN COATING COMPOUNDS
DE10126149A1 (en) 2001-05-30 2002-12-05 Mitsubishi Polyester Film Gmbh Opaque colored, hydrolysis-resistant, biaxially oriented film made of a crystallizable thermoplastic and process for its production
MXPA04007399A (en) 2002-02-01 2006-02-24 Johnson Polymer Llc Oligomeric chain extenders for processing, post-processing and recycling of condensation polymers, synthesis, compositions and applications.
US20040147678A1 (en) 2003-01-29 2004-07-29 Clariant International, Ltd. Solid concentrate composition for polymeric chain extension
DE102004024196A1 (en) 2004-05-13 2005-12-01 Basf Ag Carbodiimides containing urea groups and silane groups
JP2007023100A (en) 2005-07-13 2007-02-01 Kureha Corp Aliphatic polyester resin composition
EP2686297A2 (en) * 2011-03-18 2014-01-22 Basf Se Use of oligomeric carbodiimides as stabilizers

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0628541A1 (en) * 1993-06-08 1994-12-14 BASF Aktiengesellschaft Carbodiimides and/or oligomeric polycarbodiimides based on 1,3-bis-(1-methyl-1-isocyanatoethyl)-benzene, process for their preparation and their use as stabilizer against hydrolysis
CN1232820A (en) * 1998-03-06 1999-10-27 巴斯福股份公司 Carbodiimides and their preparation
CN101928446A (en) * 2008-11-11 2010-12-29 三菱聚酯薄膜有限公司 Biaxially oriented hydrolysis resistant polyester film and method for production of same and use of same
CN101955633A (en) * 2009-05-15 2011-01-26 三菱聚酯薄膜有限公司 Biaxially stretched polyester film containing a decarboxylation catalyst and method for production of same and use of same in electrical insulation applications

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109971007A (en) * 2019-04-01 2019-07-05 江南大学 A kind of normal-temperature solidification polyurethane class anti-fog thin film and preparation method thereof
CN109971007B (en) * 2019-04-01 2021-05-28 江南大学 Normal-temperature curing polyurethane anti-fog film and preparation method thereof

Also Published As

Publication number Publication date
EP2780407A1 (en) 2014-09-24
WO2013072310A1 (en) 2013-05-23
JP2014533752A (en) 2014-12-15
IN2014CN03735A (en) 2015-09-04
KR20140103956A (en) 2014-08-27

Similar Documents

Publication Publication Date Title
CN103946291A (en) Additives for the hydrolytic stabilisation of polycondensates
US20130131255A1 (en) Additives for stabilizing polycondensates with respect to hydrolysis
CN105899573A (en) Copolycarbonate and composition comprising same
JP2016505088A (en) Polymer resin composition excellent in impact resistance or heat resistance
KR20130044867A (en) Blend of polyester and polycarbonate
NL1016364C2 (en) Refractory thermoplastic resin composition.
WO2011043187A1 (en) Eyeglasses molded article, process for production of same, and eyeglasses
EP3170852B1 (en) Copolycarbonate resin and preparation method therefor
KR101537860B1 (en) Polycarbonate composite increased gamma-radiation resistant property and molded article using same
WO2013073818A1 (en) Polylactic acid resin and copolymer polyester resin blend, and molded product using same
KR101670551B1 (en) Polycarbonate resin composition with improved compatibility having good scratch resistance and transparency and product thereof
KR101768319B1 (en) Biodegradable resin composition and preparing method of the same
CN102295763B (en) Poly lactic acid resin, resin composition, and resin molding
JP5415395B2 (en) Polycarbonate resin composition
KR101164145B1 (en) Polycarbonate resin composition with superior scratch resistance
CN107207857A (en) Polyarylene sulfide composition with excellent metal adhesive
CN106398136B (en) A kind of low-viscosity polyester engineering plastics and preparation method thereof for NMT technology
KR20170026888A (en) Thermoplastic resin composition and article comprising the same
WO2007022902A1 (en) Polycarbonate moulding compound exhibiting improved rheological properties
JPH0339348A (en) Thermoplastic resin composition
KR101424882B1 (en) Polycarbonate resin composition having good scratch resistance and transparency
KR101737013B1 (en) Copolymer Polyester Resin Composition and Molding Comprising the Same
KR20220048550A (en) Polycarbonate resin composition, method for preparing the resin composition and molding article comprising the same
KR101666412B1 (en) Polycarbonate resin composition with high flowability and improved chemical resistance and strength under low temperature, showing excellent thermal stability under processing with long cycle time and method for preparing the same
KR101334347B1 (en) Multiwall sheet and its composition by copolyester/polycarbonate alloy, and preparing method for them

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20140723